KR930006081B1 - Process for preparing acrylic group resin having good heat resistance and transparency - Google Patents
Process for preparing acrylic group resin having good heat resistance and transparency Download PDFInfo
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Description
본 발명은 내열성이 우수한 투명 아크릴계 수지의 제조방법에 관한 것으로서, 더 상세하게는 메타크릴수지와 이미드화 물질을, 이미드화 반응성을 향상시키는 촉매 존재하에서 반응시켜, 내열성이 우수한 투명 아크릴계 수지를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a transparent acrylic resin having excellent heat resistance, and more particularly, to prepare a transparent acrylic resin having excellent heat resistance by reacting a methacryl resin and an imidized material in the presence of a catalyst for improving imidization reactivity. It is about a method.
종래, 메타크릴수지는 투명성, 내후성 및 기계적 성질이 우수하여 고성능 광학소재, 장식소재, 자동차, 전기제품 등에 이용되었다. 그러나, 메타크릴수지는 열변형 온도가 100℃이하로 낮기 때문에 내열성이 요구되는 분야에 사용의 한계가 나타나 내열성 향상의 필요성이 나타나게 되었다.Conventionally, methacryl resin has been used in high performance optical materials, decorative materials, automobiles, electrical appliances, etc. because of its excellent transparency, weather resistance, and mechanical properties. However, since the methacrylic resin has a low heat deformation temperature of 100 ° C. or lower, the use of methacrylic resin is limited in fields requiring heat resistance, and thus the need for improvement of heat resistance appears.
메타크릴수지의 내열성을 향상시키는 방법으로는, 1) 아크릴산, 메타크릴산 또는 이들의 에스테르 중합체와 제1급 아민을 비등점이 높은 용매 존재하에서 가열하여 반응시키는 방법(미합중국 특허 제2146209호), 2) 메타크릴수지를 물 존재하에서 제1급 아민과 반응시키는 방법(미합중국 특허 제3284425호), 3) 메타크릴수지와 암모니아 또는 제1급 아민을 압출기중에서 반응시키는 방법(미합중국 특허 제4246374호), 4) 메타크릴수지와 액화된 암모니아 또는 제1급 아민을 용매 존재하에서 반응시키는 방법(일본 특허공고 소63-36696호)등이 제안되고 있다.As a method of improving the heat resistance of methacrylic resins, 1) acrylic acid, methacrylic acid or ester polymers thereof and primary amines are heated and reacted in the presence of a high boiling point solvent (US Pat. No. 2146209), 2 3) a method of reacting methacryl resin with primary amine in the presence of water (US Pat. No. 3284425), 3) a method of reacting methacryl resin with ammonia or primary amine in an extruder (US Pat. No. 4246374), 4) A method of reacting methacryl resin with liquefied ammonia or primary amine in the presence of a solvent (Japanese Patent Publication No. 63-36696) has been proposed.
그러나, (1)의 방법에서는 사용되고 있는 용매의 비점이 높기 때문에 생성한 이미드화 중합체로부터 용매의 완전한 분리가 상업적 규모에서 곤란하며, 이 결과 얻어진 이미드화 중합체가 착색되어 생성 중합체의 투명성을 저하시킨다. 또 (2)의 방법에서는 다량의 물을 분산매로 사용하여 이미드화 반응시킴으로 물층과 중합체층이 분리되어 균일한 이미드화 중합체를 얻기 어렵고, 반응의 아클릴 중합체의 연화점 이상에서 일어나므로 반응 생성물의 덩어리가 교반측에 엉겨붙어 취급하기 어려우며, (3)의 방법에서는 고점도인 중합체의 이미드화 반응이 가스상의 제1급 아민과 행하여지기 때문에 균일한 중합체를 얻기 어렵다. 또한 (4)의 방법에서는 무수 조건에서 촉매의 사용없이 반응이 이루어짐으로 반응속도가 늦게 되어 실질적으로 고온(230~250℃이상)에서 6시간 반응시간이 소요되고 있어 생성중합체 및 반응 중합체의 고온 장시간 체류에 의한 변색 및 고분자 열분해가 일어나 물성의 저하가 나타나며, 생산비용이 증대되는 등의 문제점이 있다.However, in the method of (1), since the boiling point of the solvent used is high, complete separation of the solvent from the resulting imidized polymer is difficult on a commercial scale, and the resulting imidized polymer is colored to reduce the transparency of the resulting polymer. In the method of (2), imidation reaction is carried out using a large amount of water as a dispersion medium, so that the water layer and the polymer layer are separated, so that a uniform imidized polymer cannot be obtained. Is entangled on the stirring side and difficult to handle, and in the method of (3), it is difficult to obtain a uniform polymer because the imidization reaction of the polymer having high viscosity is performed with the gaseous primary amine. In addition, in the method of (4), the reaction is slow without the use of a catalyst under anhydrous conditions, and the reaction rate is substantially lower, and the reaction time is required for 6 hours at a high temperature (230-250 ° C. or more). There is a problem such as discoloration and polymer pyrolysis due to the retention, resulting in a decrease in physical properties and an increase in production cost.
따라서, 본 발명에서는 상기와 같은 문제점을 개선한 것으로, 첫째는, 메틸메타크릴레이트 중합체와 이미드화 물질로 제1급 아민, 또는 제1급 아민을 생성시키는 암모니아 화합물과 반응할 때 반응성을 증가시키기 위하여 촉매를 첨가하여, 무수물 조건하에서 내열성이 우수한 투명성 아크릴계 수지를 제조하는 것과, 둘째는, 반응물과 생성물이 용해될 수 있는 용매를 사용하여 균일하게 반응을 이룸으로 균일하게 이미드화한 메틸메타크릴이미드 중합체를 제조하여 아크릴계 수지 본래의 우수한 광학적 성질, 기계적 성질, 내후성, 성형 가공성, 생산성 등의 모든 특성을 제하시키지 않고, 투명성이 우수한 내열성 아크릴계 수지를 제조하는 방법에 관한 것이다.Accordingly, the present invention improves the above problems, firstly, to increase the reactivity when reacted with a methyl methacrylate polymer and an imidized material to produce a primary amine, or an ammonia compound that produces a primary amine. In order to prepare a transparent acrylic resin having excellent heat resistance under anhydride conditions by adding a catalyst, and secondly, methyl methacryl which is imidized uniformly by uniform reaction using a solvent in which reactants and products can be dissolved. The present invention relates to a method for producing a heat-resistant acrylic resin having excellent transparency without producing a mid-polymer and not lowering all the properties such as the excellent optical properties, mechanical properties, weather resistance, molding processability, and productivity of the acrylic resin.
즉, 본 발명은 메타크릴수지에 제1급 아민 또는 제1급 아민을 발생시키는 암모니아 화합물을, 용매 존재하에서, 촉매를 0.01~15중량% 첨가하여 100~350℃온도로 반응시킴을 특징으로 하는 내열성 투명 아크릴계 수지 제조방법에 관한 것이다.That is, the present invention is characterized by reacting the ammonia compound that generates the primary amine or the primary amine to the methacryl resin in the presence of a solvent by adding 0.01 to 15% by weight of a catalyst and reacting at a temperature of 100 to 350 ° C. It relates to a heat-resistant transparent acrylic resin production method.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
메타크릴수지에 일반식(Ⅰ)로 나타나는 제1급 아민 또는 제1급 아민을 발생시키는 암모니아 화합물, 일반식(Ⅱ)로 나타나는 암모니움 바이카보네이트 및 이의 유도체와 이미드화 반응 촉진제로서 일반식(Ⅲ)으로 나타나는 테트라알킬암모니움 하이드록사이드를 첨가하여 용매 존재하에서 균일하게 반응시킴으로써, 메타크릴수지에 다음 일반식(Ⅳ)로 나타내는 이미드 구조를 도입하여 메타크릴아미드그룹을 함유하는 중합체를 제조하는 것으로, 메타크릴아미드그룹을 바람직하게는 5중량% 이상, 함유하는 중합체를 제조하는 것이다.Ammonia compound which generates primary amine or primary amine represented by general formula (I) to methacryl resin, ammonium bicarbonate represented by general formula (II) and derivatives thereof and general formula (III) By adding tetraalkylammonium hydroxide represented by) and reacting uniformly in the presence of a solvent, an imide structure represented by the following general formula (IV) was introduced into methacryl resin to prepare a polymer containing methacrylamide group. The polymer containing methacrylamide group, Preferably it is 5 weight% or more.
상기식에서, R은 수소원자, 또는 탄소원자 1 내지 20의 치환되거나 비치환된 알킬, 시클로알킬, 아릴, 알카릴, 아르알킬 또는 알릴기를 나타낸다.Wherein R represents a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl, aryl, alkaryl, aralkyl or allyl group of 1 to 20 carbon atoms.
본 발명에서 메타크릴이미드그룹 함유 중합체는 메타크릴이미드(디메틸글루타르이미드) 구조가 메타크릴수지의 측쇄중에 도입된 것이다.In the present invention, the methacrylic imide group-containing polymer is a methacrylic imide (dimethylglutarimide) structure is introduced into the side chain of the methacrylic resin.
여기에서 이미드 단위를 도입하는 메타크릴수지는 메틸메타크릴레이트 단일 중합체 및 메틸메타크릴레이트와 공중합체는 이룰수 있는 에틸렌계 불포화 단량체, 예를들어 메타크릴산 에스테르, 아크릴산 에스테르, 스티렌 또는 α-메틸스티렌 그리고 무수말레이산 등과의 메타크릴성 공중합체 등이 메타크릴이미드그룹 함유 공중합체를 생성하기 위한 메타크릴성 수지로서 사용될 수 있다. 따라서 가장 바람직하게는 메틸메타크릴레이트 단일 중합체, 메틸메타크릴레이트와 메틸아크릴레이트 공중합체, 메틸메타크릴레이트와 공중합체 및 메틸메타크릴레이트, 스티렌 그리고 무수말레인산 공중합체가 언급될 수 있다.The methacrylate resin in which the imide unit is introduced here is a copolymer of methyl methacrylate homopolymer and methyl methacrylate, which can be formed from ethylenically unsaturated monomers such as methacrylic acid ester, acrylic acid ester, styrene or α-methyl. Methacrylic copolymers with styrene, maleic anhydride and the like can be used as the methacrylic resin for producing the methacrylic imide group-containing copolymer. Thus, most preferably, methyl methacrylate homopolymer, methyl methacrylate and methyl acrylate copolymer, methyl methacrylate and copolymer and methyl methacrylate, styrene and maleic anhydride copolymer may be mentioned.
상기 언급된 공중합체에서 메틸메타크릴레이트 단위의 함량이 특별히 한정된 것은 아니지만, 메틸메타크릴레이트 단위의 함량이 적어도 50중량% 이상의 것이 바람직하다.Although the content of methyl methacrylate units in the above-mentioned copolymer is not particularly limited, it is preferable that the content of methyl methacrylate units is at least 50% by weight or more.
메타크릴산 에스테르로서는, 예를들어 메틸메타크릴레이트, 에틸메타크릴레이트, 프로필메타크릴레이트, n-부틸메타크릴레이트, 이소부틸메타크릴레이트, t-부틸메타크릴레이트, 시클로헥실메타크릴레이트, 벤질메타크릴레이트, 아릴메타크릴레이트가 언급될 수 있다. 또 아크릴산 에스테르로서는 메탈아크릴리레이트, 이소부틸아크릴레이트, t-부틸아크릴레이트, 시클로헥실아크릴레이트, 벤질아크릴레이트, 아릴아크릴레이트가 언급될 수 있다. 바람직하기로는 투명도 및 이미드화 반응 관점에서 메틸메타크릴레이트의 단독 중합체가 바람직하다.As methacrylic acid ester, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, Benzyl methacrylate, aryl methacrylate may be mentioned. In addition, as the acrylic acid esters, metal acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate and aryl acrylate may be mentioned. Preferably, the homopolymer of methyl methacrylate is preferable from the viewpoint of transparency and imidization reaction.
본 발명에 사용된 반응 촉매로는 무수물 조건의, 테트라알킬암모니움 하이드록사이드가 적당하다. 바람직하게는 테트라메틸암모니움 하이드록사이드(25% 알코올 용액)가 적당하다. 테트라알킬암모니움 하이드록사이드는 반응계에서 염기성 촉매로 작용을 하여 반응 중합체의 반응성을 증가시켜 줌으로 중합체의 이미드화율을 증가시키고, 상대적으로 반응조건(반응온도 및 반응압력)을 완화시켜 줌으로 보다 내열성이 우수한 투명 아크릴계 수지를 제조할 수 있다. 또한 테트라알킬암모니움 하이드록사이드는 가열에 의하여 트리알킬아민과 알코올로 분해되므로 중합체로부터의 분리가 용이하다. 따라서, 메틸메타크릴이미드 중합체 제조시 테트라알킬암모니움 하이드록사이드는 0.01~15중량%, 더 바람직하기로는 0.1~7중량%의 범위이다.As the reaction catalyst used in the present invention, tetraalkylammonium hydroxide in anhydride conditions is suitable. Preferably tetramethylammonium hydroxide (25% alcohol solution) is suitable. Tetraalkylammonium hydroxide acts as a basic catalyst in the reaction system to increase the reactivity of the reacting polymer, thereby increasing the imidation rate of the polymer and relatively relaxing the reaction conditions (reaction temperature and reaction pressure). The transparent acrylic resin which is more excellent in heat resistance can be manufactured. In addition, since tetraalkylammonium hydroxide is decomposed into trialkylamine and alcohol by heating, separation from the polymer is easy. Accordingly, the tetraalkylammonium hydroxide in the preparation of the methylmethacrylimide polymer is in the range of 0.01 to 15% by weight, more preferably 0.1 to 7% by weight.
테트라알킬암모니움 하이드록사이드가 0.01중량% 이하에서는, 촉매의 양이 너무 희박하여 촉매효과가 나타나지 않으며, 15중량% 이상에서는 촉매의 효과가 떨어져 물성의 저하를 나타낸다.When the tetraalkylammonium hydroxide is 0.01% by weight or less, the amount of the catalyst is too lean so that no catalytic effect appears. At 15% by weight or more, the effect of the catalyst is lowered, indicating a drop in physical properties.
본 발명에 사용된 용매는 고분자 측쇄간 축합반응에 의해 이루어지는 이미드화 반응을 저해하지 않고, 또 부분 이미드화 반응의 경우, 메타크릴산 또는 메틸메타크릴테이트 세그멘트부에 변화를 부여하지 않는 것이 필요하다. 더욱이 균일하게 반응으로 균일한 이미드화 중합체를 얻기 위하여 반응물인 아크릴레이트 중합체, 이미드화 물질 및 반응 생성물인 이미드그룹 함유 중합체를 용해할 수 있을 용매가 필요하다. 또한 용매의 끓는 점이 너무 높으면 반응종료 후 용매의 제거가 어려우며, 너무 낮으면 압력이 상승하게 되므로 끓는점이 50~160℃정도의 용매가 바람직하다.The solvent used in the present invention does not inhibit the imidization reaction caused by the polymer side chain condensation reaction, and in the case of partial imidization reaction, it is necessary not to impart a change to the methacrylic acid or methyl methacrylate segment. . Furthermore, in order to obtain a uniform imidized polymer by uniform reaction, a solvent capable of dissolving the reactant acrylate polymer, the imidized material and the imide group-containing polymer which is the reaction product is required. In addition, if the boiling point of the solvent is too high, it is difficult to remove the solvent after the completion of the reaction, if too low, the pressure is increased, so the boiling point is a solvent of about 50 ~ 160 ℃.
메타크릴수지, 메타크릴이미드그룹 함유 중합체의 용매로는 벤젠, 톨루엔, 크실렌 등의 방향족 탄화수소화합물, 메틸에틸케톤, 에틸렌글리콜 디메틸에테르, 다이글라임, 다이옥산, 테트라하이드로퓨란등의 케톤, 에테르계 화합물, 메틸알코올, 에틸알코올, 이소프로필알코올, 부틸알코올 등의 알코올류 그리고 디메틸포름아미드, 디메틸술폭시드, 디메틸아세트아미드 등의 단독 또는 혼합용매가 사용되고 있다.Examples of solvents for the methacryl resin and the methacrylimide group-containing polymer include aromatic hydrocarbon compounds such as benzene, toluene, and xylene, methyl ethyl ketone, ethylene glycol dimethyl ether, diglyme, dioxane, and ketones such as tetrahydrofuran and the like. Compounds, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, and single or mixed solvents such as dimethylformamide, dimethyl sulfoxide and dimethylacetamide are used.
메틸메타크릴레이트 중합체를 이미드화 시키는 이미드화 물질로는 제1급 아민으로서의 암모니아, 메틸아민, 에틸아민, n-프로필아민, n-부틸아민, 헵틸아민, 헥실아민, 시클로헥실아민, 옥틸아민, 노닐아민, 데실아민, 도데실아민, 헥사데실아민, 옥타데실아민, 이소부틸아민, sec-부틸아민, t-부틸아민, 이소프로필아민, 2-에틸헥실아민, 2-페닐에틸아민, 아릴아민, 알라닌, 벤진아민, 파라클로로벤질아민, 디메톡시페닐에틸아민, 아닐린, 브로모아닐린, 트리클로로아닐린 등이 사용되며, 제1급 아민을 발생시키는 암모니아 화합물로는 우레아, 1,3-디메틸우레아 1,3-디에틸우레아, 암모니움 아세테이트, 암모니움 바이카보네이트 및 이외 유도체가 사용된다.The imidation material which imidates the methyl methacrylate polymer includes ammonia as the primary amine, methylamine, ethylamine, n-propylamine, n-butylamine, heptylamine, hexylamine, cyclohexylamine, octylamine, Nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, isobutylamine, sec-butylamine, t-butylamine, isopropylamine, 2-ethylhexylamine, 2-phenylethylamine, arylamine , Alanine, benzineamine, parachlorobenzylamine, dimethoxyphenylethylamine, aniline, bromoaniline, trichloroaniline, and the like, and ammonia compounds generating primary amines include urea, 1,3-dimethylurea 1,3-diethylurea, ammonium acetate, ammonium bicarbonate and other derivatives are used.
반응기 내에서 메틸메타크릴레이트 수지와 이미드화 물질과의 반응온도는 100℃이상 350℃이하가 적당하며, 더욱이 150℃이상 300℃미만이 좋다. 반응온도가 350℃이상에서는 메틸메타크릴레이트 중합체의 분해 반응이 일어나게 되며, 100℃이하에서는 이미드화 반응속도가 현저하게 저하되어 이미드 구조를 함유하는 중합체를 제조하는데 반응시간이 길어지게 된다.The reaction temperature of the methyl methacrylate resin and the imidized material in the reactor is preferably from 100 ° C to 350 ° C, and more preferably from 150 ° C to 300 ° C. When the reaction temperature is 350 ° C. or more, the decomposition reaction of the methyl methacrylate polymer occurs, and below 100 ° C., the imidization reaction rate is remarkably lowered, resulting in a longer reaction time for preparing a polymer containing an imide structure.
본 발명에 있어서, 중합체의 특성 측정법은 다음에 의해 측정하였으며, 측정법은 하기의 실시예에 적용된다.In the present invention, the measurement method of the properties of the polymer was measured by the following, and the measurement method is applied to the following examples.
1) 중합체 이미드화 적외선 스펙트럼(BIORAD제, FTIR)을 이용한 브롬화칼륨(KBr)펠렛상으로 측정하였다.1) Measurement was carried out on potassium bromide (KBr) pellets using a polymer imidized infrared spectrum (manufactured by BIORAD, FTIR).
2) 중합체의 이미드화 양(%)의 측정은 원소분석 값(PERKIN ELMER MODEL : 240B)의 질소 함유량에 의해 계산하였다.2) The measurement of the amount of imidization (%) of the polymer was calculated by the nitrogen content of the elemental analysis value (PERKIN ELMER MODEL: 240B).
3) 내열성은 유리 전이온도(Dupont Model : 1090)를 측정하여 검토하였다.3) The heat resistance was examined by measuring the glass transition temperature (Dupont Model: 1090).
본 발명을 하기의 실시예로 상세히 설명하면 다음과 같다.The present invention will be described in detail with reference to the following Examples.
[실시예 1]Example 1
충분히 건조시킨 메틸메타크릴레이트 중합체[(주)럭키 IH-830]100중량부, 이미드화 물질로 시클로헥실아민 57중량부, 촉매로서 테트라메틸암노니움 하이드록사이드(메탄올중 25%) 8.2중량부, 용매로서 무수조건의 테트라하이드로퓨란 455중량부, 무수조건의 메틸알코올 55중량부를 1.8리터의 고온, 고압용 오토클레이브 반응기에 넣어 반응물을 교반하면서 산화방지를 위하여 질소를 충분히 환류시킨 후 반응물을 250rpm으로 교반하여, 반응물을 용해시켜 190℃에서 3시간(내압 250psi)반응을 진행하였다.100 parts by weight of a sufficiently dried methyl methacrylate polymer [Lucky IH-830], 57 parts by weight of cyclohexylamine as an imidized substance, 8.2 parts by weight of tetramethylamnonium hydroxide (25% in methanol) as a catalyst In addition, 455 parts by weight of anhydrous tetrahydrofuran and 55 parts by weight of anhydrous methyl alcohol were added to a 1.8 liter high-temperature, high-pressure autoclave reactor to stir the reactants while sufficiently refluxing nitrogen to prevent oxidation. After stirring at 250 rpm, the reactants were dissolved, and the reaction was performed at 190 ° C. for 3 hours (250 psi internal pressure).
반응종료 후 메틸메타크릴이미드그룹 함유 중합체가 포함된 용액을 n-헥산에 재 침전한 후 여과하여 100℃감압 건조기 중에서 충분히 건조하여 흰색분말 중합체를 얻었다. 여기서 얻어진 중합체를 적외선 스펙트럼으로 측정한 결과 1680㎝-1, 1720㎝21에서 메틸메타클리이미드 구조 특성띠를 확인하여 메틸메타크릴아미드 중합체를 확인하였다. 이 중합체의 물성 측정결과는 표 1에 나타내었다.After completion of the reaction, the solution containing the methyl methacrylimide group-containing polymer was re-precipitated in n-hexane, filtered and dried sufficiently in a 100 ° C. reduced pressure dryer to obtain a white powder polymer. The polymer obtained here was measured by infrared spectrum, and the methylmethacrylamide structural characteristic band was confirmed at 1680 cm -1 and 1720 cm 21 to confirm the methyl methacrylamide polymer. The measurement results of the physical properties of this polymer are shown in Table 1.
[실시예 2]Example 2
충분히 건조시킨 메틸메타크릴레이트 중합체[(주)럭키 IH-830]100중량부, 이미드화 물질로 프로필아민 37중량부, 반응촉매로 테트라메틸암모니움 하이드록사이드 (메탄올중 25%) 용매로서 테트라하이드로퓨란 455중량부, 메틸알코올 55중량부, 반응온도가 190℃(내압 300psi)인 것을 제외하고는 실시예 1과 동일하게 제조하였으며, 이들의 물성을 표 1에 나타내었다.100 parts by weight of a sufficiently dried methyl methacrylate polymer [Lucky IH-830], 37 parts by weight of propylamine as an imidized material, and tetramethylammonium hydroxide as a reaction catalyst (25% in methanol) as a solvent. 455 parts by weight of hydrofuran, 55 parts by weight of methyl alcohol, was prepared in the same manner as in Example 1 except that the reaction temperature is 190 ℃ (inner pressure 300 psi), their physical properties are shown in Table 1.
[실시예 3]Example 3
메틸메타크릴레이트(MMA) 57중량%, 무수말레인산(MAH) 27중량% 및 스티렌(ST) 16중량%, 분자량 조절제로 t-도데실 메르캅탄올 0.2중량% 첨가하여 145℃에서 2시간 동안 용액 중합(용매로는 에틸벤젠)을 하여 공중합체를 얻었다.57% by weight of methyl methacrylate (MMA), 27% by weight of maleic anhydride (MAH) and 16% by weight of styrene (ST), 0.2% by weight of t-dodecyl mercaptanol as a molecular weight modifier and solution at 145 ° C for 2 hours Polymerization (ethylbenzene as a solvent) was carried out to obtain a copolymer.
여기서 얻은 충분히 건조시킨 MMA-MAH-ST 공중합체 100중량부에, 이미드화 물질로서 시클로헥실아민 68중량부, 촉매로서 테트라메틸암모니움 하이드록사이드 6.9중량부 반응온도가 190℃(내압 260psi) 메탈알코올 46중량부인 것을 제외하고는 실시예 1과 동일하게 제조하였으며, 이들의 물성을 표 1에 나타내었다.68 parts by weight of cyclohexylamine as an imidized substance, 6.9 parts by weight of tetramethylammonium hydroxide as a catalyst, and 100 parts by weight of a sufficiently dried MMA-MAH-ST copolymer obtained at a reaction temperature of 190 ° C (260 psi). Except for 46 parts by weight of alcohol was prepared in the same manner as in Example 1, their physical properties are shown in Table 1.
[실시예 4]Example 4
실시예 3에서 제조한 충분히 건조시킨 MMA-MAH-ST 100중량부에, 이미드화 물질로 프로필아민, 촉매로서 테트라메틸암모니움 하이드록사이드 6.9중량부, 용매로서 테트라하이드로퓨란 382중량부, 메틸알코올 46중량부, 반응온도가 190℃(내압 300psi)인 것을 제외하고는 실시예 1과 동일하게 제조하였으며, 이들의 물성을 표 1에 나타내었다.100 parts by weight of sufficiently dried MMA-MAH-ST prepared in Example 3, 6.9 parts by weight of propylamine as an imidized substance, catalyst as tetramethylammonium hydroxide, 382 parts by weight of tetrahydrofuran as solvent, and methyl alcohol 46 parts by weight and the reaction temperature was prepared in the same manner as in Example 1 except that 190 ℃ (inner pressure 300 psi), and their physical properties are shown in Table 1.
[실시예 5]Example 5
반응온도가 210℃(내압 400psi)인 것을 제외하고는 실시예 1과 동일한 조건에서 시료를 제조하였으며, 이들의 물성은 표 1에 나타내었다.Samples were prepared under the same conditions as in Example 1 except that the reaction temperature was 210 ° C. (400 psi), and their physical properties are shown in Table 1.
[실시예 6]Example 6
반응온도가 210℃(내압 450psi)인 것을 제외하고는 실시예 2과 동일한 조건에서 시료를 제조하였으며, 이들의 물성은 표 1에 나타내었다.Samples were prepared under the same conditions as in Example 2 except that the reaction temperature was 210 ° C (inner pressure 450 psi), and their physical properties are shown in Table 1.
[실시예 7]Example 7
반응온도가 210℃(내압 450psi)인 것을 제외하고는 실시예 3과 동일한 조건에서 시료를 제조하였으며, 이들의 물성은 표 1에 나타내었다.Samples were prepared under the same conditions as in Example 3 except that the reaction temperature was 210 ° C. (inner pressure 450 psi), and their physical properties are shown in Table 1.
[실시예 8]Example 8
반응온도가 210℃(내압 450psi)인 것을 제외하고는 실시예 4과 동일한 조건에서 시료를 제조하였으며, 이들의 물성은 표 1에 나타내었다.Samples were prepared under the same conditions as in Example 4 except that the reaction temperature was 210 ° C (inner pressure 450 psi), and their physical properties are shown in Table 1.
[비교예 1~8][Comparative Examples 1-8]
이미드화 물질을 첨가하지 않은 것을 제외하고는 실시예 1~8과 동일한 조건에서 시료를 제조하였으며, 이들의 물성을 표 1에 나타내었다.Samples were prepared under the same conditions as in Examples 1 to 8 except that no imidized material was added, and their physical properties are shown in Table 1.
[표 1]TABLE 1
Claims (7)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900012454A KR930006081B1 (en) | 1990-08-13 | 1990-08-13 | Process for preparing acrylic group resin having good heat resistance and transparency |
| EP91900956A EP0461224B1 (en) | 1989-12-29 | 1990-12-28 | A process for the preparation of heat resistant and transparent acrylic resin |
| PCT/KR1990/000023 WO1991009886A1 (en) | 1989-12-29 | 1990-12-28 | A process for the preparation of heat resistant and transparent acrylic resin |
| US07/773,896 US5369189A (en) | 1989-12-29 | 1990-12-28 | Process for the preparation of heat resistant and transparent acrylic resin |
| JP3501368A JP2607789B2 (en) | 1989-12-29 | 1990-12-28 | Method for producing heat-resistant transparent acrylic resin |
| DK91900956.3T DK0461224T3 (en) | 1989-12-29 | 1990-12-28 | Process for producing heat-resistant and transparent acrylic resin |
| ES91900956T ES2091905T3 (en) | 1989-12-29 | 1990-12-28 | A PROCEDURE FOR THE PREPARATION OF A TRANSPARENT, HEAT RESISTANT ACRYLIC RESIN. |
| DE69028521T DE69028521T2 (en) | 1989-12-29 | 1990-12-28 | METHOD FOR PRODUCING HEAT-RESISTANT AND TRANSPARENT ACRYLIC RESIN |
| AT91900956T ATE142653T1 (en) | 1989-12-29 | 1990-12-28 | METHOD FOR PRODUCING HEAT RESISTANT AND TRANSPARENT ACRYLIC RESIN |
| GR960402912T GR3021538T3 (en) | 1989-12-29 | 1996-11-06 | A process for the preparation of heat resistant and transparent acrylic resin |
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